Carbonation of Mg-rich minerals offers an intriguing candidate carbon sequestration process technology, which can provide large-scale CO{sub 2} disposal. Such disposal bypasses many long-term storage problems by (i) providing containment in the form of mineral carbonates that have proven stable over geological time, (ii) generating only environmentally benign materials, and (iii) essentially eliminating the need for continuous site monitoring. The primary challenge for viable process development is reducing process cost. This is the primary focus of the CO{sub 2} Mineral Sequestration Working Group managed by Fossil Energy at DOE, which includes members from the Albany Research Center, Los Alamos National Laboratory, the National Energy Technology Laboratory, Penn State University, Science Applications International Corporation, and the University of Utah, as well as from our research group at Arizona State University. Carbonation of the widely occurring mineral olivine (e.g., forsterite, Mg{sub 2}SiO{sub 4}) is a leading process candidate, which converts CO{sub 2} into the mineral magnesite (MgCO{sub 3}). As olivine carbonation is exothermic, it offers intriguing low-cost potential. Recent studies at the Albany Research Center have found aqueous-solution carbonation is a promising approach. Cost effectively enhancing carbonation reactivity is central to reducing process cost. Many of the mechanisms that impact reactivity occur at the solid/solution interface. Understanding these mechanisms is central to the ability to engineer new and modified processes to enhance carbonation reactivity and lower cost. Herein, we report the results of our UCR I project, which focused on exploring the reaction mechanisms that govern aqueous-solution olivine carbonation using model olivine feedstock materials. Carbonation was found to be a complex process associated with passivating silica layer formation, which includes the trapping of magnesite nanocrystals within the passivating silica layers, cracking and exfoliation of the layers, silica surface migration, olivine etch pit formation, transfer of the Mg and Fe in the olivine into the product carbonate, and the nucleation and growth of magnesite crystals on/in the silica/olivine reaction matrix. These phenomena occur in concert with the large solid volume changes that accompany the carbonation process, which can substantially impact carbonation reactivity. Passivating silica layer formation appears to play a major role in inhibiting carbonation reactivity. New approaches that can mitigate the effectiveness of passivating layer formation may offer intriguing potential to enhance carbonation reactivity and lower process cost.
